EP0522163B1 - Composition de resine polyolefinique modifiee - Google Patents

Composition de resine polyolefinique modifiee Download PDF

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Publication number
EP0522163B1
EP0522163B1 EP91906579A EP91906579A EP0522163B1 EP 0522163 B1 EP0522163 B1 EP 0522163B1 EP 91906579 A EP91906579 A EP 91906579A EP 91906579 A EP91906579 A EP 91906579A EP 0522163 B1 EP0522163 B1 EP 0522163B1
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weight
polyolefin resin
resins
parts
epoxy group
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EP0522163A4 (en
EP0522163A1 (fr
Inventor
Toru 3-101 Kohpo Seya Ueki
Masaji 4-31 Mitsui Toatsu Apartment Yoshimura
Kazuharu 3-33 Mitsui Toatsu Apartment Kanezaki
Susumu 5-30-3 Natsumi Kishi
Takashi 3-29 Mitsui Toatsu Apartment Satoh
Minoru 4-5-45 Dai Takiguchi
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Mitsui Toatsu Chemicals Inc
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Mitsui Toatsu Chemicals Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present invention relates to a modified polyolefin resin composition which does not give out a bad smell during modification and which has excellent adhesion to fillers, metals and polymeric resin substrates as well as a thermoplastic resin composition comprising the modified polyolefin resin and a thermoplastic resin and having good mechanical properties.
  • polyolefin resins have excellent physical and chemical properties and have widely been used as materials for molding into, for instance, fibers and films. Moreover, they are reinforced with fillers such as glass fibers for making the best use of these characteristics.
  • polyolefins have low adhesion to glass fibers and thus it is not possible to sufficiently enjoy reinforcing effects of fillers, because they are free of reactive functional groups.
  • modified polyolefin resins such as those obtained through copolymerization of olefins with modifying agents, for instance, unsaturated carboxylic acids or epoxy group-containing vinyl monomers such as glycidyl methacrylate (hereinafter referred to as "GMA") or allyl glycidyl ether, or grafting polyolefin resin with the modifying agents (see, for instance, Japanese Unexamined Patent Publication (hereinafter referred to as "J.P. KOKAI”) No. Sho 59-62613) and EP-A-0 317 358.
  • modifying agents for instance, unsaturated carboxylic acids or epoxy group-containing vinyl monomers such as glycidyl methacrylate (hereinafter referred to as "GMA") or allyl glycidyl ether, or grafting polyolefin resin with the modifying agents
  • J.P. KOKAI Japanese Unexamined Patent Publication
  • polyolefin resins with other resins such as polyester resins, polyphenylene sulfide resins, polycarbonate resins and polyamide resins since they are excellent in impact resistance and resistance to chemicals and are not expensive.
  • the polyolefin resin in itself has low compatibility with the foregoing resins. Accordingly, the resulting blend shows substantial reduction of such properties as Izod impact strength, tensile strength and elongation and is not impracticable.
  • An object of the present invention is to provide a modified polyolefin resin composition which does not give out a bad smell during modification and which has excellent adhesion to fillers, metals and substrates of synthetic resins.
  • Another object of the present invention is to provide a thermoplastic resin composition
  • a thermoplastic resin composition comprising a modified polyolefin resin and other thermoplastic resins and having good mechanical properties such as Izod impact strength, tensile strength and elongation.
  • a still another object of the present invention is to provide a modified polyolefin resin composition which is reinforced with fillers.
  • the foregoing polyolefin resin is obtained by a method which comprises reacting the epoxy group-containing acrylamide monomer represented by the above general formula I with a polyolefin resin in the presence of a free-radical initiator in an extruder.
  • thermoplastic resin composition which comprises 5 to 95% by weight of the foregoing modified polyolefin resin and 95 to 5% by weight of another thermoplastic resin.
  • a filler-reinforced polyolefin resin composition which comprises 100 parts by weight of the foregoing modified polyolefin resin and 3 to 300 parts by weight of an inorganic or organic filler.
  • polystyrene resins examples include polypropylene, polyethylene, propylene-ethylene block or random copolymers, ethylene-propylene elastomer, ethylene-propylene-diene elastomer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene ethylidene norbornene copolymer and poly(4-methyl-pentene-1).
  • the foregoing resins may be used in combination.
  • the epoxy group-containing acrylamide monomer represented by the foregoing general formula I used as the modifying agent in the present invention can easily be prepared by condensing an aromatic hydrocarbon carrying at least one phenolic hydroxyl group with N-methylolacrylamide or N-methylolmethacrylamide, or an alkyl ether derivative of N-methylolacrylamide or N-methylolmethacrylamide in the presence of an acid catalyst and then converting the phenolic hydroxyl groups into glycidyl groups.
  • epoxy group-containing acrylamide monomer examples include N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]acrylamide, N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]methacrylamide and N-[4-(2,3-epoxypropoxy)-3-methylbenzyl]acrylamide.
  • the free-radical initiator usable in the invention may be any conventionally known ones and specific examples thereof are organic peroxy compounds represented by t-butylperoxy benzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butyl-peroxide and 2,5-dimethyl-2,5-di(t-butylperoxy)hexene-3; azobisnitrile compounds represented by azo bisisobutyronitrile and azobisisovalelonitrile; or organic peroxy compounds represented by benzoin peroxide.
  • organic peroxy compounds represented by t-butylperoxy benzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butyl-peroxide and 2,5-dimethyl-2,5-di(t-butylperoxy)hexene-3
  • the preparation of the modified polyolefin resin is carried out using 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight of an epoxy group-containing acrylamide monomer of Formula I and 0.005 to 5 parts by weight, preferably 0.01 to 1 part by weight of a free-radical initiator per 100 parts by weight of a polyolefin.
  • the method of the preparation is not restricted to particular ones and any known method may be adopted.
  • the reaction is performed at the decomposition temperature of the free-radical initiator used while stirring the mixture of an acrylamide monomer, a radical-forming agent and a polyolefin resin in an organic solvent.
  • reaction can also be performed by uniformly mixing these starting materials in a high-speed stirring machine and then, melting and kneading the mixture in a single strew or multi-screw extruder having a sufficient kneading ability.
  • the reaction temperature and time preferably range from 150 to 250°C and 0.5 to 30 minutes respectively. It is preferred to prepare the modified polyolefin resin according to the method in which an extruder is used, from the economical standpoint.
  • the modified polyolefin resin of the present invention may be used in the form of a composition further containing an unmodified polyolefin resin.
  • the content of such an unmodified polyolefin resin ranges from 0 to 95% by weight and preferably 0 to 80% by weight.
  • a preferred proportion of each components in the filler-reinforced polyolefin resin composition of the present invention is 3 to 300 parts by weight, preferably 5 to 200 parts by weight of a filler per 100 parts by weight of a modified polyolefin resin or a resin mixture comprising the modified polyolefin resin and an unmodified polyolefin resin. If the amount of the filler is less than the lower limit, sufficient physical properties-improving effect cannot be ensured, while if it exceeds the upper limit, coloration of the resin is caused and the impact strength of the resulting composition is lowered.
  • the fillers usable in the present invention include, for instance, metallic materials such as metals, e.g., iron, aluminum, copper, lead, zinc, tin and nickel and alloys mainly comprising these metals (for instance, stainless steel and brass) and a variety of metal oxides; as well as inorganic or organic materials such as glass, carbon fibers, carbon black, silicon carbide fibers, carbon whisker, asbestos, graphite, magnesium carbonate, calcium carbonate, clay, mica, talc, silica, barium sulfate, alumina, inorganic pigments, wood powder, pulp and polyester fibers.
  • metallic materials such as metals, e.g., iron, aluminum, copper, lead, zinc, tin and nickel and alloys mainly comprising these metals (for instance, stainless steel and brass) and a variety of metal oxides
  • inorganic or organic materials such as glass, carbon fibers, carbon black, silicon carbide fibers, carbon whisker, asbestos, graphite, magnesium carbonate, calcium carbonate, clay
  • the filler-reinforced polyolefin resin composition can be prepared by uniformly mixing a polyolefin resin, an epoxy group-containing acrylamide monomer, a free-radical initiator and a filler in a high-speed stirring machine and then, melting and kneading the mixture in a single screw or multi-screw extruder having a sufficient kneading ability.
  • a method in which a polyolefin resin, an epoxy group-containing acrylamide monomer, a free-radical initiator and a filler are simultaneously melt and kneaded a method in which a filler is subsequently added to a mixture of other ingredients prepared in advance; or a method comprising coating a filler with a molten composition comprising a polyolefin resin, an epoxy group-containing acrylamide monomer and a free-radical initiator.
  • thermoplastic resin composition which comprises 5 to 95 parts by weight, preferably 10 to 90 parts by weight of the modified polyolefin resin and 95 to 5 parts by weight, preferably 90 to 10 parts by weight of another thermoplastic resin
  • examples of said another thermoplastic resin(other than the modified polyolefins) are polyester resins, polyphenylene sulfide resins, polycarbonate resins, polyamide resins, polyacetal resins, polyphenylene oxide resins, polyallylate resins and polysulfone resins.
  • polyester resins used herein are preferably polyesters having aromatic rings in the chain units thereof, which are polymers or copolymers obtained through condensation reactions of aromatic dicarboxylic acids and diols as principal components.
  • polyester resins are polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclo hexylenedimethylene terephthalate and polyethylene-2,6-naphthalate as well as polybutylene terephthalate elastomers such as "HIGHTREL” (available from Du Pont-Toray Co., Ltd.).
  • the polyphenylene sulfide resin herein means a crosslinking type PPS which requires crosslinking after the polymerization for converting them into high molecular weight ones and a high molecular weight linear type PPS.
  • PPS polyphenylene sulfide resin
  • Examples of polyphenylene sulfide resins commercially available include “RYTON P-6” (available from Phillips Petroleum Company) for the crosslinking type PPS and "FORTRON W-205" (available from Kureha Chemical Industry Co., Ltd.) for the linear type PPS's.
  • the polycarbonate resins are prepared by reacting divalent phenols with carbonate precursors such as phosgene, halogen formate (haloformate) or carbonate esters. Homopolymers derived from bisphenol A are preferably used.
  • polyamide resins examples include nylon 6, nylon 66, nylon 46, nylon 11 and nylon 12 and, particularly nylon 6 and nylon 66 are preferred because of high heat resistance and good moldability thereof.
  • thermoplastic resin composition containing the modified polyolefin resin according to the present invention may also be prepared by simultaneously uniformly mixing a polyolefin resin, another thermoplastic resin, an epoxy group-containing acrylamide monomer and a radical-forming agent and then melting and kneading the resulting mixture in an extruder.
  • the thermoplastic resin composition may further comprise, depending on purposes, reinforcing materials such as a variety of elastomers, pigments, dyes, glass fibers, metals and carbon fibers; fillers such as talc and calcium carbonate; antioxidants, UV absorbers, lubricants, flame-retardants and antistatic agents; and electrically conductive fillers such as carbon black.
  • a polypropylene resin manufactured and sold by Mitsui Toatsu Chemicals, Inc. under the trade name of NOBLEN JS-G
  • N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl ]acrylamide available from Kanegafuchi Chemical Industry Co., Ltd.
  • dicumyl peroxide were blended in the amounts listed in the following Table 1 and mixed in a Henschel mixer. Then the resulting mixtures were extruded into pellets at a melting temperature of 200°C and the number of screw-revolutions of 100 rpm in a twin-screw extruder (having the screw diameter of 30 mm and an L/D of 30) to give modified polypropylene resins.
  • the peel strength of the resulting modified polypropylene resins applied onto an Al plate, a steel plate and an EVOH sheet was determined.
  • the results obtained are listed in Table 1 together with the smell observed during extrusion.
  • the data listed in Table 1 indicate that these modified polypropylene resins did not give out any bad smell during extrusion, had sufficient peel strength and thus, had good adhesion.
  • Example 2 The same procedure as in Example 1 was repeated except that radical-forming agents or epoxy group-containing acrylamide monomers were not added.
  • the resulting resins were subjected to IR spectroscopic analysis after Soxhlet extraction with chloroform. As a result, it was found that an absorption peak (1650 cm ⁇ 1) to be ascribed to the carbonyl derived from amide groups was disappeared. This clearly indicates that the acrylamide monomer was not radical-added to the polypropylene resin.
  • the peel strength of the resulting modified polypropylene resins was determined in the same manner as in Example 1. The results obtained are listed in Table 1. These modified polypropylene resins did not give out any bad smell during extrusion, but had a low peel strength and thus had insufficient adhesion.
  • Example 3 The same procedures as in Example 3 was repeated except that acryl glycidyl ether (AGE) was substituted for the epoxy group-containing acrylamide monomer used therein.
  • AGE acryl glycidyl ether
  • Table 1 This resin gave out a bad smell during extrusion and had a low peel strength.
  • a polyethylene resin manufactured and sold by Mitsui Petrochemical Industries, Ltd. under the trade name of HIGHZEX 2200J
  • N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]methacrylamide available from Kanegafuchi Chemical Industry Co., Ltd.
  • 1,3-bis-(t-butylperoxy-isopropyl)benzene were blended in the amounts listed in the following Table 2 and extruded into pellets in the same manner as in Example 1 to give modified polyethylene resins.
  • the results of the IR spectroscopic analysis indicate that the methacrylamide monomer was radical-added to the polyethylene resin.
  • Example 5 The same procedures as in Example 5 was repeated except that free-radical initiators or epoxy group-containing acrylamide monomers were not added. These resins were subjected to IR spectroscopic analysis after Soxhlet extraction with chloroform. As a result, it was found that the epoxy group-containing acrylamide monomer was not radical-added to the polyethylene resin.
  • the peel strength of the resulting modified polyethylene resins was determined in the same manner as in Example 1. The results obtained are listed in Table 2 together with the smells observed during extrusion thereof. These modified polyethylene resins did not give out any bad smell during extrusion, but had a low peel strengths.
  • a polypropylene resin manufactured and sold by Mitsui Toatsu Chemicals, Inc. under the trade name of MITSUI NOBLEN JS-G
  • N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]acrylamide available from Kanegafuchi Chemical Industry Co., Ltd.
  • dicumyl peroxide as a free-radical initiator and glass chopped strands having length of 3 mm were charged and mixed in a tumbling mixer in the amounts listed in the following Table 3.
  • Example 9 The same procedures as in Example 9 was repeated except that the amounts of the acrylamide monomers or free-radical initiators were outside the range defined according to the present invention. The results obtained are summarised in Table 3. These resins had a low heat resistance or mechanical strength.
  • Example 11 The same procedure as in Example 11 was repeated except that maleic anhydride (MAH) was substituted for the acrylamide monomer.
  • MAH maleic anhydride
  • Table 3 The results obtained are summarised in Table 3.
  • the resulting resin was inferior in physical properties to the resin obtained through the use of the acrylamide monomer and gave out a bad smell during extrusion.
  • a polyethylene terephthalate (manufactured and sold by Mitsui Pet Resin Co., Ltd. under the trade name of J 025) as a polyester resin, ethylene-propylene-dicyclopentadiene elastomer resin (manufactured and sold by Japan Synthetic Rubber Co., Ltd. under the trade name of EP 86) as a polyolefin resin, N-[4-(2,3-epoxypropoxy) -3,5-dimethylbenzyl]acrylamide as an acrylmide monomer and dicumyl peroxide as a free-radical initiator were charged and mixed in a Henschel mixer in amounts listed in the following Table 4.
  • the resulting mixture was extruded into pellets at a melting temperature of 260 °C and the number of screw-revolutions of 100 rpm in a twin-screw extruder (having a screw diameter of 30 mm and an L/D of 30).
  • the pellets of these resins were injection-molded into test pieces and physical properties thereof were determined. The results obtained are listed in Table 4.
  • the resulting resins had physical properties in which impact resistance, rigidity and heat resistance were well-balanced.
  • a polybutylene terephthalate (manufactured and sold by Teijin Co., Ltd. under the trade name of TRB-H) and a polybutylene terephthalate elastomer (manufactured and sold by Du Pont-Toray Co., Ltd. under the trade name of HIGHTREL 5557) as polyester resins, propylene-ethylene block copolymer resin (manufactured and sold by Mitsui Toatsu Chemicals, Inc.
  • a polypropylene resin manufactured and sold by Mitsui Toatsu Chemicals, Inc. under the trade name of MITSUI NOBLEN JS-G; 100 parts by weight
  • N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]acrylamide available from Kanegafuchi Chemical Industry Co., Ltd.; 1 part by weight
  • dicumyl peroxide 0.1 part by weight
  • the modified polypropylene resin, the foregoing polypropylene resin and a polybutylene terephthalate (manufactured and sold by Teijin Chemical Industry Co., Ltd. under the trade name of TRB-H) were mixed in a ratio shown in Table 6 and extruded into pellets in the foregoing twin-screw extruder at a melting temperature of 250°C and the number of screw-revolutions of 100 rpm.
  • the pellets of these resins were injection-molded into test pieces and physical properties thereof were determined in the foregoing manner. The results obtained are listed in Table 6. All of these resins had sufficient mechanical properties practically acceptable.
  • Example 23 The same procedure as in Example 23 was repeated except that the modified polypropylene resin was not used and physical properties of the resulting resins were determined according to the same method. The results obtained are listed in Table 6. The resulting resins had low mechanical properties practically unacceptable.
  • a polyethylene resin manufactured and sold by Mitsui Petrochemical Industries, Ltd. under the trade name of MITSUI HIGHZEX 2200J; 100 parts by weight
  • N-[ 4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]methacrylamide available from Kanegafuchi Chemical Industry Co., Ltd.; 1 part by weight
  • 1,3-bis-(t-butylperoxy-isopropyl) benzene 0.3 part by weight
  • the modified polyethylene resin, the foregoing polyethylene resin and polycarbonate resin (manufactured and sold by Teijin Co., Ltd. under the trade name of PANLITE L-1225) were mixed in ratios shown in Table 7 and extruded into pellets in the foregoing twin-screw extruder at the melting temperature of 250°C and the number of screw-revolutions of 100 rpm.
  • the pellets of these resins were injection-molded into test pieces and physical properties thereof were determined in the foregoing manner. The results obtained are listed in Table 7. All of these resins had sufficient mechanical properties practically acceptable.
  • Example 26 The same procedures as in Example 26 was repeated except that the modified polyethylene resin was not used and physical properties of the resulting resins were determined according to the same method. The results obtained are listed in Table 7. The resulting resins had low mechanical properties practically unacceptable.
  • a propylene-ethylene block copolymer resin manufactured and sold by Mitsui Toatsu Chemicals, Inc. under the trade name of MITSUI NOBLEN BEB-G; 100 parts by weight
  • N-[4-(2,3-epoxypropoxy)-3-methylbenzyl] acrylamide available from Kanegafuchi Chemical Industry Co., Ltd.; 3 parts by weight
  • dicumyl peroxide 2 parts by weight
  • the modified propylene-ethylene block copolymer resins and a polyphenylene sulfide resin (manufactured and sold by Kureha Chemical Industry Co., Ltd. under the trade name of FORTRON W-205) were mixed in ratios shown in Table 8 and extruded into pellets in the foregoing twin-screw extruder at a melting temperature of 310 °C and the number of screw-revolutions of 100 rpm.
  • the pellets of these resins were injection-molded into test pieces and physical properties thereof were determined in the foregoing manner. The results obtained are listed in Table 8. All of these resins had sufficient mechanical properties practically acceptable.
  • Example 29 The same procedure as in Example 29 was repeated except that the modified propylene-ethylene block copolymer resin was not used and physical properties of the resulting resins were determined according to the same method. The results obtained are listed in Table 8. The resulting resins had substantially low mechanical properties practically unacceptable.
  • a polypropylene as (MITSUI NOBLEN BJH-G, available from Mitsui Toatsu Chemicals, Inc.; 100 parts by weight), N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]acrylamide (available from Kanegafuchi Chemical Industry Co., Ltd.; 1 part by weight) and dicumyl peroxide (0.1 part by weight) were mixed in a Henschel mixer and then extruded into pellets at a melting temperature of 200 °C and the number of screw-revolutions of 100 rpm in a twin-screw extruder (having a screw diameter of 30 mm and an L/D of 30) to give modified polypropylene resins.
  • MITSUI NOBLEN BJH-G available from Mitsui Toatsu Chemicals, Inc.
  • N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]acrylamide available from Kanegafuchi Chemical Industry Co., Ltd
  • the modified polypropylene resins the foregoing polypropylene resin and a nylon 9 resin (manufactured and sold by Toyobo Co., Ltd. under the trade name of T-802) were mixed in rates listed in Table 9 and extruded into pellets in the foregoing twin-screw extruder at a melting temperature of 250 °C and the number of screw-revolutions of 100 rpm.
  • the pellets of these resins were injection-molded into test pieces and physical properties thereof were determined in the foregoing manner. The results obtained are listed in Table 9. All of these resins had sufficient mechanical properties practically acceptable.
  • Example 32 The same procedure as in Example 32 was repeated except that the modified polypropylene resin was not used and physical properties of the resulting resins were determined according to the same method. The results obtained are listed in Table 9. The resulting resins had very low mechanical properties practically unacceptable.
  • a polypropylene resin (MITSUI NOBLEN JH-G, available from Mitsui Toatsu Chemicals, Inc.; 100 parts by weight), N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]acrylamide (available from Kanegafuchi Chemical Industry Co., Ltd.; 2 parts by weight) and dicumyl peroxide (0.3 part by weight) were mixed in a Henschel mixer and then, modified polypropylene resins were prepared in the same manner as in Example 32.
  • the modified polypropylene resins, the foregoing polypropylene resin and a polybutylene terephthalate resin manufactured and sold by Teijin Ltd.
  • Example 35 The same procedure as in Example 35 was repeated except that the modified polypropylene resin was not used and physical properties of the resulting composition were determined according to the same method. The results obtained are listed in Table 10. The resulting composition had very low mechanical properties practically unacceptable.
  • a polypropylene resin (the same resin as in Example 1; 100 parts by weight), N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]acrylamide (1 part by weight) and dicumyl peroxide (0.05 part by weight) were dry-blended in a Henschel mixer and treated in the same manner as in Example 23 to give a modified polypropylene resin.
  • the epoxy group content and reaction amount rate of the modifying agent which reacted with the polypropylene resin were determined as follows.
  • reaction mass was subjected to Soxhlet extraction with chloroform for 20 hours and then washed to remove the unreacted epoxy group-containing acrylamide monomer, the oligomers thereof, the radical-forming agent and the decomposition products thereof remaining after the reaction.
  • Example 38 The same procedure as in Example 38 was repeated to give a modified polypropylene resin except that glycidyl methacrylate (GMA) was substituted for the N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]acrylamide in an amount of three times that of the latter in order to control the epoxy group content after modification to that observed in Example 38.
  • GMA glycidyl methacrylate
  • This modified polypropylene resin was treated in the same manner as in Example 38 to give test pieces and physical properties thereof were determined. The results obtained are listed in Table 11.
  • Example 38 The same procedure as in Example 38 was repeated except that any modifying agent was not used and physical properties were determined. The results thus obtained are summarized in Table 11.
  • Example 26 27 28 23 24 25 Modified Polyethylene Resin ( % by weight ) 15 20 45 Polyethylene Resin ( % by weight ) 10 30 40 15 50 85 Polycarbonate Resin ( % by weight ) 75 50 15 85 50 15 Izod Impact Strength (kg ⁇ cm/cm) 30 22 25 15 10 12 Tensile Strength ( kg/cm2 ) 430 350 300 380 280 250 Elongation ( % ) 15 75 150 4 15 30 TABLE 8 Composition Example Comp.
  • Example 29 30 31 26 27 28 Ethylene-Propylene Block Copolymer Resin ( % by weight ) 15 50 85 Modified Ethylene-Propylene Block Copolymer Resin ( % by weight ) 15 50 85 Polyphenylene Sulfide Resin ( % by weight ) 85 50 15 85 50 15 Izod Impact Strength (kg ⁇ cm/cm) 6 7 15 2 3 4 Tensile Strength ( kg/cm2 ) 750 510 390 730 470 320 Elongation ( % ) 20 35 150 3 5 8 TABLE 9 Composition Example Comp.
  • Example 32 33 34 29 30 31 Modified Polypropylene Resin ( % by weight ) 10 25 50 Polypropylene Resin ( % by weight ) 15 25 35 25 50 85 Polyamide Resin ( % by weight ) 75 50 15 75 50 15 Izod Impact Strength (kg ⁇ cm/cm) 19 8 12 3 3 5 Tensile Strength ( kg/cm2 ) 430 380 310 400 350 300 Elongation ( % ) 25 75 130 7 8 8 TABLE 10 Composition Example Comp.
  • Example 35 36 37 32 33 34 Modified Polypropylene Resin ( % by weight ) 15 20 75 Polypropylene Resin ( % by weight ) 10 30 10 25 50 85 Polybutylene Terephthalate Resin ( % by weight ) 75 50 15 75 50 15 Glass Fiber (part by weight per 100 parts by weight of the foregoing resins) 5 30 100 5 30 100 Izod Impact Strength (kg ⁇ cm/cm) 8 6 11 4 3 3 3 3 3
  • the modified polyolefin resin composition according to the present invention does not give out any bad smell during modification, is excellent in adhesion to inorganic fillers, metals and polymeric resin substrates and, good mechanical properties such as Izod impact strength, tensile strength and elongation. Therefore, the resin composition can be used in the fields of automobiles, appliances and industrial parts and has enough practical value.

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Claims (12)

  1. Résine de polyoléfine modifiée, obtenue par la réaction, en présence d'un amorceur générateur de radicaux libres, d'une résine de polyoléfine avec un acrylamide monomère contenant un groupe époxyde et représentée par la formule générale I suivante :

            H₂C = CR-CO-NH-CH₂-Ar     I

    formule dans laquelle Ar représente un groupe hydrocarboné aromatique ayant 6 à 24 atomes de carbone, qui porte comme substituant(s) au moins un groupe glycidyloxy, et R représente un atome d'hydrogène ou un groupe méthyle.
  2. Résine de polyoléfine modifiée selon la revendication 1, qui comprend en outre 0 à 95 % en poids d'une résine de polyoléfine non modifiée.
  3. Résine de polyoléfine modifiée selon la revendication 1, dans laquelle la résine de polyoléfine est choisie parmi du polypropylène, du polyéthylène, des copolymères à blocs ou statistiques de propylène-éthylène, un polymère élastomère d'éthylène-propylène, un polymère élastomère d'éthylène-propylène-diène, un copolymère d'éthylène-propylène-dicyclopentadiène, un copolymère d'éthylène-propylène-éthylidène norbornène et du poly(4-méthyl-pentène-1).
  4. Résine de polyoléfine modifiée selon la revendication 1, dans laquelle l'acrylamide monomère contenant un groupe époxyde est choisi parmi le N-[4-(2,3-époxypropoxy)-3,5-diméthylbenzyl]acrylamide, le N-[4-(2,3-époxypropoxy)-3,5-diméthylbenzyl]méthacrylamide et le N-[4-(2,3-époxypropoxy)-3-méthylbenzyl]acrylamide.
  5. Procédé pour préparer une résine de polyoléfine modifiée, comprenant la réaction, en présence d'un amorceur générateur de radicaux libres, dans une extrudeuse, d'une résine de polyoléfine avec un acrylamide monomère contenant un groupe époxyde, monomère représenté par la formule générale I suivante :

            H₂C = CR-CO-NH-CH₂-Ar     (I)

    formule dans laquelle Ar représente un groupe hydrocarboné aromatique ayant 6 à 24 atomes de carbone, qui porte comme substituant(s) au moins un groupe glycidyloxy, et R représente un atome d'hydrogène ou un groupe méthyle.
  6. Procédé selon la revendication 5, dans lequel on utilise 100 parties en poids de la résine de polyoléfine, 0,01 à 20 parties en poids de l'acrylamide monomère contenant un groupe époxyde et représenté par la formule générale I ci-dessus, et 0,005 à 5 parties en poids de l'amorceur générateur de radicaux libres.
  7. Procédé selon la revendication 5, dans lequel la température de réaction se situe entre 150 et 250°C.
  8. Composition de résine thermoplastique comprenant 5 à 95 % en poids d'une résine de polyoléfine modifiée obtenue par la réaction d'une résine de polyoléfine avec un acrylamide monomère contenant un groupe époxyde et représenté par la formule générale I, telle que définie à la revendication 1, en opérant en présence d'un amorceur générateur de radicaux libres, et 95 à 5 % en poids d'une autre résine thermoplastique.
  9. Composition de résine thermoplastique selon la revendication 8, dans laquelle ladite autre résine thermoplastique est choisie parmi des résines de polyester, des résines de poly(sulfure de phénylène), des résines de polycarbonate, des résines de polyamide, des résines de polyacétal, des résines de poly(oxyde de phénylène), des résines de polyallylate et des résines de polysulfone.
  10. Composition de résine de polyoléfine renforcée par une charge d'armature, comprenant 100 parties en poids d'une résine de polyoléfine modifiée obtenue par la réaction, en présence d'un amorceur générateur de radicaux libres, d'une résine de polyoléfine avec un acrylamide monomère contenant un groupe époxyde, monomère représenté par la formule générale I telle que définie à la revendication 1, et 3 à 300 parties en poids d'une charge.
  11. Composition de résine de polyoléfine modifiée, obtenue par le chauffage jusqu'à fusion et le malaxage de (A) 10 à 90 % en poids d'une résine de polyoléfine, (B) 90 à 10 % en poids d'une autre résine thermoplastique ; et 0,01 à 20 parties en poids d'un acrylamide monomère contenant un groupe époxyde et représenté par la formule générale I, telle que définie à la revendication 1, et 0,005 à 5 parties en poids d'un amorceur générateur de radicaux libres, respectivement pour 100 parties en poids de la somme des constituants (A) et (B) ci-dessus.
  12. Composition de résine de polyoléfine renforcée par une armature de charge, que l'on obtient en faisant fondre et en malaxant 100 parties en poids d'une résine de polyoléfine, 0,01 à 20 parties en poids d'un acrylamide monomère contenant un groupe époxyde et représenté par la formule générale I, telle que définie à la revendication 1, 0,005 à 5 parties en poids d'un amorceur générateur de radicaux libres et 3 à 300 parties en poids d'une charge.
EP91906579A 1990-03-28 1991-03-27 Composition de resine polyolefinique modifiee Expired - Lifetime EP0522163B1 (fr)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP7658190 1990-03-28
JP76581/90 1990-03-28
JP7658090 1990-03-28
JP76580/90 1990-03-28
JP164037/90 1990-06-25
JP16403790 1990-06-25
JP20751590 1990-08-07
JP207515/90 1990-08-07
PCT/JP1991/000393 WO1991014717A1 (fr) 1990-03-28 1991-03-27 Composition de resine polyolefinique modifiee

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EP0522163A1 EP0522163A1 (fr) 1993-01-13
EP0522163A4 EP0522163A4 (en) 1993-02-03
EP0522163B1 true EP0522163B1 (fr) 1996-06-05

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EP (1) EP0522163B1 (fr)
KR (1) KR960003932B1 (fr)
AT (1) ATE138942T1 (fr)
DE (1) DE69120062T2 (fr)
WO (1) WO1991014717A1 (fr)

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DE69130664D1 (de) * 1990-04-28 1999-02-04 Kanegafuchi Chemical Ind Modifiziertes olefinpolymerisat, verfahren zur herstellung und harzzusammensetzung, die dieses polymer enthält
US5728791A (en) * 1990-11-30 1998-03-17 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Polyvinyl graft-polymers and manufacturing method thereof
US5436297A (en) * 1992-10-30 1995-07-25 Tonen Corporation Modified polyolefin
JP3264773B2 (ja) * 1993-12-28 2002-03-11 ダイセル化学工業株式会社 熱可塑性樹脂組成物
EP0779307A4 (fr) * 1995-06-30 1998-12-16 Kanegafuchi Chemical Ind Copolymere ethylene-acetate de vinyle greffe et composition de resine le contenant
US5709948A (en) * 1995-09-20 1998-01-20 Minnesota Mining And Manufacturing Company Semi-interpenetrating polymer networks of epoxy and polyolefin resins, methods therefor, and uses thereof
US5690873A (en) * 1995-12-11 1997-11-25 Pall Corporation Polyarylene sulfide melt blowing methods and products
US6110589A (en) * 1995-12-11 2000-08-29 Pall Corporation Polyarylene sulfide melt blown fibers and products
US6130292A (en) * 1995-12-11 2000-10-10 Pall Corporation Polyarylene sulfide resin composition
EP1630201B1 (fr) * 2003-06-05 2014-12-10 Toray Industries, Inc. Compositions de resine de polysulfure de phenylene
US8273825B2 (en) * 2007-03-20 2012-09-25 Sabic Innovative Plastics Ip B.V. Polycarbonate/polyolefin based resin compositions and their production processes and uses
JP5234011B2 (ja) * 2010-01-07 2013-07-10 豊田合成株式会社 金属と樹脂との複合体の製造方法

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FR1326931A (fr) * 1961-06-28 1963-05-10 Hoechst Ag Procédé de préparation de copolymères d'oléfines saturés greffés avec l'acrylamide
JPS5853935A (ja) * 1981-09-28 1983-03-30 Tokyo Ink Kk プラスチツクス・金属用導電性熱融着性樹脂組成物
JPS5962613A (ja) * 1982-10-01 1984-04-10 Showa Denko Kk 変性ポリオレフインの製造方法
JPS60130580A (ja) * 1983-12-15 1985-07-12 Kanegafuchi Chem Ind Co Ltd 新規グリシジル化合物及びその製造方法
JPS62129345A (ja) * 1985-11-30 1987-06-11 Japan Synthetic Rubber Co Ltd 熱可塑性樹脂組成物
JPS62129343A (ja) * 1985-11-30 1987-06-11 Japan Synthetic Rubber Co Ltd 熱可塑性樹脂組成物
JPS6337109A (ja) * 1986-07-31 1988-02-17 Kanegafuchi Chem Ind Co Ltd グリシジル基を有する新規重合体およびその製造方法
JPS63225619A (ja) * 1986-12-15 1988-09-20 Kanegafuchi Chem Ind Co Ltd 樹脂組成物及びそれを用いた反応成形方法
CA1326093C (fr) * 1987-11-20 1994-01-11 Yoshiki Toyoshima Resine polyolefinique modifiee

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KR930700561A (ko) 1993-03-15
KR960003932B1 (ko) 1996-03-23
WO1991014717A1 (fr) 1991-10-03
ATE138942T1 (de) 1996-06-15
US5349027A (en) 1994-09-20
DE69120062T2 (de) 1997-02-06
EP0522163A4 (en) 1993-02-03
EP0522163A1 (fr) 1993-01-13
DE69120062D1 (de) 1996-07-11

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